Detergent containing beta, beta&#39;-decylaminobisethanolpropionamide



DETERGENT CONTAINIVG fiLV-DECYLAMINOBIS- ETHANOLPROPIONAMIDE Lloyd F. Henderson, Fair Lawn, and Charles H. Schrarnm, Hillsdale, N. J., assignors to Lever Brothers Company, New York, N. Y., a corporation of Maine No Drawing. ApplicationAugust 10, 1955.

Serial No. 527,635

13 Claims. (Cl. 252153) This invention relates to light duty detergent compositions which can be formulated either as liquid solutions or as powders and which contain a small amount of 6,,8'-decylaminobis-ethanolpropionamide to improve the sudsing and detergency of the compositions.

There are two general types of detergent compositions available on the market: light duty and heavy duty detergents. Heavy duty detergents have the ability to remove stubborn soil and prevent soil redeposition in laundering. These are all-purpose detergents, usually are available in powdered form, and contain polyphosphates as builders. However these detergents by virtue of their polyphosphate content and their strong detergency tend to irritate sensitive skin and therefore are less favored by the housewife for dishwashing and fine attractive to the housewife because there is no need to dissolve the detergent. A washing solution is obtainable simply upon dilutionof an easily measured portion of the concentrated liquid# with water. However, liquid detergents present a special problem.

a deterioration in performance due to separation of active ingredients. A cloudy or two-phase solution containing precipitated solids has little sales appeal on the store shelf. This requirement complicates the'obtention of a highly concentrated detergent solution, and makes it diflicult to formulate a liquid detergent which is competitive with a dry powdered product, for special solubility requirements arily used in dilute solutions.

It is imperative that the liquid detergent solution be highly concentrated in order to keep at a minimum the volume of solvent in the concentrate, to make it possible to use small measured portions for each wash. From a marketing standpoint the concentration of the liquid detergent should be such that the package of liquid detergent is roughly equivalent to a package of dry powdered detergent and is of convenient size. From 12 to 16 ounces of liquid detergent should be approximately equal in use properties to a 19 to 20 ounce package of the equivalent dry powdered light duty detergent.

An important feature of the light duty detergent is its sudsing power. Most housewives who wash dishes based upon this is the time when yield of crude methyl 6,5-decylaminobispropionate vCe the suds no longer completely cover the surface of the washing solution. As is well known, most synthetic detergents are deficient in sudsing power, and this diffi permit the preparation of solutions of high concentrations. The solubility of this agent in the solvents used in liquid detergents thus is an important property of such agents. Many such agents are very sparsely" solublein water;

In accordance with the invention, synthetic detergent compositions are provided whichcontain 3, 8'-de'cyl aminobis-ethanolpropionamide and 'an organic nonsoap detergent. Inasmuch as the detergent ,B, 3'-decylarninobis-ethanolpropionainide will of course be present in an them.

@F-Decylaminobis-ethanolpropionamide is a new compound which is not described in the literature:

It is prepared by reacting decylamine with methyl acrylate to form methyl ,8,,8-decylaminodipropionate, which then is reacted with ethanolamine to form fi,;3 '-decylaminobis-ethanolpropionamide. The reaction is shown by the following sequence of reactions:

CxoHnNH: 2CH 2= CHCOOCH CHzCHzCOOCH| CwHn IQNHZCHICHQOH CHgCHzCONHOITaCHzOH C10H2l CHrCHzCONHCHzCHzQH 2 mols of the methyl acrylate and 2 mols of the ethanolamine are required.

The reaction with the methyl acrylate is carried out by refluxing the necessary amounts of the starting materials. The reaction with the ethanolamine is carried out by simply mixing, followed byheating on a steam bath until reaction is complete, which will require about 24 hours. The following illustrates the procedure.

EXAMPLE A One hundred fifty-seven grams of decylamine were refluxed with 344 grams of methyl acrylate for 20 hours. The excess acrylate was removed by distillation. The

was quantitative and the material was of sufiicient purity for use in the next step.

250 grams of the methyl fi,/i-decylaminopropionate thus obtained was reacted with 120 grams of ethanolamine at to C. for 12 hours. A quantitative yield of the fi,/3'-decylaminobis-ethanolpropionamide was obtained.

amount to completely dissolve 1 Enough of the 5,p'-decylaminobis-ethanolpropionamide would beused to. enhance sudsing and/or detergency of the synthetic detergent in aqueous solutions of washing concentrations. Usually from 2% to is adequate. sThe alkyl aryl sulfonates are a class of anionic synthetic detergents well known in the art under this name. They have the general structure wherein R is a straight or branched chain hydrocarbon radical having from 1 to about 24 carbon atoms, at least one R having 8 to 24 carbon atoms, 2: is a number from 1 to 5, and may be an average number, and M is hydrogen, an alkali metal or an organic amine cation. R can for example be methyl, ethyl, hexyl, isohexyl, octyl, tert-octyl, isooctyl, decyl, dodecyl, or octadecyl, One example thereof are the sulfonated polypropylene benzene alkanes, having an alkyl radical characterized by the branched chain structure of polypropylene and ata tertiary alkyl carbon to the benzene ring, and

tached by having the following general structure:

RrCHCHaR:

where M is hydrogen, an alkali metal or an organic amine cation, and R and R are alkyl, of the type formula C,,H and at least one R is a straight or branched chain polypropylene group, the whole alkyl group containing preferably twelve to fifteen carbon atoms. These are known compounds, whose preparation and properties are set forth in U. S. Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in commerce under the trade names Oronite, Ultrawet and Neolene.

Another example thereof are the alkyl aryl sulfonates made by chlorinating a keryl hydrocarbon, and condensing this with benzene, followed by sulfonating. These are the Nacconolsf The alkyl sulfates are characterized by the structure RSO M, where M is hydrogen or an alkali metal, i. e., ammonium, sodium, orvpotassium, or an organic amine cation, and R is a straight or branched chain saturated or unsaturated hydrocarbon radical, such as myristyl, palmityl, oleic, stearyl, and lauryl, as well as the mixed alkyl radicals derived from fatty oils, such as coconut oil fatty alkyl, tallow fatty alkyl, cottonseed oil fatty alkyl and fish oil fatty alkyl radicals. R usually has from eight to eighteen carbon atoms, preferably from twelve to sixteen carbon atoms.

Another class of anionic synthetic detergents are the sulfated oxyethylated alkyl phenols, which have the following general formula:

wherein R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, A is oxygen, sulfur, a carbonamide or thiocarbonamide group or a carboxylic or thiocarboxylic ester group, x is a number from three to eight, and M is hydrogen or an alkali metal, e. g., sodium, potassium, and ammonium, oran organic amine cation. R can, for example, be a synthetic detergents are are characterized by or an alkali metal, i. e., ammonium,

or an organic amine cation, n is a from one to about five, preferably two or three, R is hydrogen, or an alkyl, aryl, or cycloaliphatic group, such as methyl, and R is an alkyl or alkylene radical, such as myristyl, palmityl, oleyl and stearyl. Sodium palmitic tauride, sodium palmitic methyl tauride, sodium myristic methyl tauride, sodium palmiticstearic methyl tauride and sodium palmitic methyl amidopropane sulfonate have been found to be particularly suitable for use in the compositions of the invention.

The anionic synthetic detergents can be used in the form of the free acid, which can be neutralized in situ in the liquid detergent solution by addition of anorganic amine or ammonium hydroxide. They are also readily available as the alkali metal salts, such as sodium, potassium and ammonium, and these would generally be used. However, the ammonium or organic amine salts may be more soluble, and in this event would be preferred, particularly from the standpoint of increasing the detergent concentration to a maximum. The amine can be any of those listed hereinafter.

There may also be used, either alone or in admixture with the anionics, nonionic synthetic detergents such as polyoxyalkylene ethers, Which'retain the terminal OH groups, as the glycols, and in which the terminal OH groups are substituted, as the mono and diethers thereof, such as the polyoxyalkylene alkyl phenols, polyoxyalkylene fatty acid amides, and alkyl polyoxyalkylene oxyand thioether and oxyand thioester nonionic detergents.

Many polyoxyalkylene glycol ether synthetic detergents havethe following general formula:

where M is hydrogen sodium, or potassium, small whole number where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an arakyl group having a straight or branched saturated or unsaturated hydrocarbon group of from eight to eighteen carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups, R and R" are hydrogen or methyl, and x is a number from eight to twenty. R can for example be a straight or branched chain octyl, nonyl, decyl, octadecyl, dodecyl, tetradecyl, or hexadecyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, octadecylbenzene, etc.

When R is alkyl it will be evident that the synthetic detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with oxide or 1,2-propylene oxide. Typical of this type of 1 alkyl ether are the condensation products of oleyl or dodecyl alcohol or mercaptan withfrom eight to sevenethylene oxide,2,3-buty1ene 1 teen moles of ethylene oxide, such as Nonic 218 and Sterox SE and esters are 61226 and Rerex of tall oil acids), Sterox CD, Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

When R is aralkyl, the synthetic detergents can be derived from an alkyl phenol or thiophenol.

The polyoxyalkylene alkyl phenols and thiophenols have the following general formula: I

Emulfor ON, SK. Typical alkyl (polyoxyethylene ester where R is a straight or branched saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to approximately eighteen carbon atoms, R and R" are hydrogen or methyl, A is or branched chain octyl, decyl, dodecyl, hexadecyl or octadecyl. Typical are the condensation products of octyl and nonyl phenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names Oronite NIW, Antarox A-400, Igepal CA and CO, Triton X100, Neutronyx 600 and Tergitol NPX.

Another class of nonionic synthetic detergents are the Pluronics, which have the structure:

These are fully described in U. S. Patent No. 2,674,619 to L. G. Lundsted, dated April 6, 1954; see especially column 3, lines 55 to 71. See also U. S. Patent No. 2,677,700 to D. R. Jackson et al., dated May 4, 1954.

' preferably is Within the range from 15 to 41, and n prefmaterials is useful.

The builder mixture is so chosen that the composition obtained in an aqueous 0.14% solution has a pH of 6 or above. Preferably, its pH lies within the range from 6 to about 10 since solutions which are more alkaline may be irritating to the skin and tend to weaken some fabrics, particularly woolens.

The powdered detergent composition is temperatures. The [3,6-decylaminobis-ethanolproprionamide may be added to the detergent composition at any stage of its manufacture, or to the finished powder.

In the case of liquid detergents the ingredients may be dissolved in warm Water, or water-and-alcohol, or alcohol; they may be dissolved separately in alcohol or Water and then these solutions are mixed. tion may be diluted to the desired concentration. amount of solvent should be suflicient to dissolve all of the solid components, and furnish a detergent solution which does not cloud or form a precipitate at temperatures as low as 45 F. The amount of total solids in the composition is variable and is limited only by the solubility of the components in the solvent. Usually, it is desirable to have the synthetic detergent concentration as high as of the syndet, as much of this as present. For optimum effects, the should be Within the range from 55%, depending upon solubility. Of this, the synthetic detergent should range from about 15% to about 50% and the concentration of the ,6,B'-clecylaminobis-ethanolpropionamide should be within the range from about 2% to about 10%.

Water is the preferred solvent. When the solid syn thetic detergent and [3,5'-decylaminobis-ethanolpropionamount of total solids about 20% to about vent properties and be tion.

Exemplifying the amines useful for these purposes, as well as for preparing salts of the anionic synthetic detergents supra, are water-soluble, strongly basic amines such as triethanolamine, diethanolamine, monoethanolamine, ethylenediamine, diethylenetriamine, tetraethanol ammonium hydroxide, morpholine, mixed isopropanolamines, monoisopropanolamine, diethylene glycol amine, and amino ethyl ethanolamine. The alkylolamines, either mono-, dior tri-, are preferred.

It may be noted that col and triethylene glycol.

The composition may also contain fumes to suit the housewifes desire. It is customary to mask the odor of organic amines, and those skilled in the art are aware of perfumes which meet this need.

The follovw'ng examples illustrate the invention.

dyestuffs and per- Exampl s 1 to 10 Ten detergent compositions were prepared having the following composition:

aerate? Lsuryl sulfate, technical, 35.5% active, trlethanolamlne salt.

Each of the compositions was dissolved in 300 p. p. m.

water and subjected to a standard dishwashing test at four different washing concentrations, as listed in the table below. These were compared with three control compositions containing the fi,fi'-decylaminobis-ethanolpropionamide and each of the synthetic detergents alone. Six-quart quantities of the solution were used in each test.

The dishwashing test determined the number of artificially soiled dinner plates washed under standardized conditions. The apparatus used was a Hobart mixer, model C-210. The dinner plates were circular, nine inches in diameter. About 5 to 5.5 grams of standard dishwashing soil was spread evenly over the top of each plate with a spatula. This soil was composed of 9 parts by weight of Covo, emulsifier free, added to 8 parts by weight of Pillsburys bread flour and 1.25 ml. of green coloring for each pound of flour used, all thoroughly mixed.

The test solution was brought to a temperature of 116 F. The plates were then washed by hand, using freshly laundered dish cloths. Washing was continued until the suds in the pan of solution no longer completely covered the surface of the water.

The dishwashing capacity of the detergent is reported in the table as the number of plates washed up to the time the end point is reached: Example Average Total Average Total No. Plates Grams Example No. Plates Grams Washed Active Washed Active M m 5 4.407 5 4.457 Control A.. g i: Control A... g a:

0. 558 0 0. 55s 31 4- 1 s 40a 25 0 Control 13.. 10 L 000 Control C 8 L 000 3 0.500 4 0.500 I 51 4. 234 48 4. 234 42 3.175 G 37 3.175 1 14 1. 05s 1. 05s 10 0.520 11 0.529 53 4.152 50 4.152 43 3.114 7 42 a. 114 2 10 1.038 19 1.038 s 0. 510 14 0. 519 50 4.117 51 4.117 45 3. 03s 8 45 3.088 3 1.020 20 1.020 11 0. 515 15 0.515 52 4.004 50 4. 094 41 3. 070 9 41 3.070 4 17 1.023 10 1.023 10 0.511 13 0.511 50 4. 043 4.043 40 3.032 m 34 a. 032 5 13 1.011 1s 1.011 10 0. 50s 11 0. 500

1 I g 1 2 Percent by weight Example No Control Con- Control A trol 2 3 4 5 C 6 7 8 9 10 B, B Decylaminobis ethanolproplonamlde 100 52. 6 35. 7 27. 1 21. 8 10 52. 6 35. 7 27. 1 21. 8 10 Ammonium Alkyl Aryl Sulfonate 100 47.4 64.3 72.9 78. 2 00 Stepanol WAT 100 47. 4 64. 3 72. 9 78. 2

v 1 37.4% active, alkyl having from 12 to 15 carbon atoms.

The dishwashing test results show that the combi- 0 nation .of the 13B-decylaminobis-ethanolpropionamide Example 11 This is an. example of a highly concentrated liquid detergent:

Example 12 The following is an additional example of a highly concentrated formulation:

Percent Sodium keryl benzene sulfonate (alkyl averaging fourteen carbon atoms, from kerosene fraction hydrocarbons) 25.0 Antaron K-460A 15.0 fi B-Decylaminobis-ethanolpropionamide 3.0 Ethyl alcohol 20.0 Water, perfume, etc 37.0

Examples 13 to 19 Seven detergent compositions were prepared having the following formulations:

Examples ela i e 19 Example N 0.

Ammonium vphenyl polypropylene sulfonate (alkyl of 12 to 15 carbon polypropylene) "percent" 35 22 22 36 0 0 mmonium salt of sulfated ethoxynated nonyl phenol (five moles ethylene oxide) percent. 0 35 13 13 0 35 0 B,fi Decylarninobis ethanolpropionamide percent. 9 9 9 3 0 0 35 Ethyl alcohol d 15 15 15 15 I 15 ater, perfume, etc 41 41 47 50 50 50 Remains clear as low as F 10 14 4 34 10 87 Solution pH 7.2 7.2 7.2 7.2 7.23 7.23

Each of the compositions was subjected to the stand- Example ardized dishwashing test of Examples 1 to 10. The following is an example of a medium-concentra- The results of the dishwashing tests were as follows: tion light duty detergent:

Percent Phenyl polypropylene sulfonic acids, ammonium NUMBER or PLATES WASHED IN 6 QTS. WATER AT 116 F Salt (alkyl 0f 12 to 15 carbon p yp py 16-63 Ammonium salt of sulfated ethoxynated nonyl 50 18Op p.m phenol, condensed with five moles of ethylene Example N oxide 10.43 pfl-Decylaminobis-ethanolpropionamide 7.00 Ethyl alcohol 20.00

49 Perfume 0.2 $3 Water, etc 45.74 43 This formulation remains clear at temperatures as low 5 as 29 F. and has a pH of 6.8. None All parts and percentages in the specification and claims are by weight, and when with reference to components of the detergent solution are based on the weight of the solution unless otherwise indicated. The compositions were subjected to standardized We claim! Washing tests in the Terg-O-Tometer, using 1250 cc. each A llght duty detergent cflmposl'tlbn Consisting of washing solutions in 180 p. p. m. water prepared by entlauy of a synthetlc f 110115031) detergent dissolving the amount of detergent indicated in the table lected flom the 1 Conslstlng 01w 311101110 and HOHIOHIC in 17 gallons of Water. Each wash was carried out at synthetlc Organic IIOIISOaP detelgents and n amount R and 90 M. for 20 minutes Eight soiled within the range from about 2 to about 10% by Weight cotton swatches (vacuum cleaner dirt) and four unsoiled of the Synthetic p detergent 0f fl B'- 3/ swatches were present in each wash The detergency was P P P to enhance the detergency and determined by examination of the soiled cotton swatches sudslng the YHthetlC nonsoap detergent. after the washing and the redeposition by examination A llght duty detergent composltlon in accordance of the unsoiled swatches after the washing. The average W 61931111} in Which h Synthetic nonsoap detergent reflectometer reading of the soiled cloth after washin 15 an amQmC Synthetlc nonsoap detergelntmlnus 30 is reported as detergent units and the average A P dutY detergen? Pmposltlon 1n accordance reflectance reading of the unsoiled cloths after washing Wlth Flalm 2 Whlch the anion: Synthetic nonsoap deter is reported as redeposition units. For comparison purgent 13 alkyl aryl sulfonateposes, typical results for a commercial polyphosphate- A llght P Y detergent omposition in accordance built alkyl aryl sulfonate detergent are included in the Wlth clan? 2 In Whlch the anlonlc Synthetic nQnSOaP table. detergent IS an alkyl sulfate.

5. A light duty detergent composition in accordance with claim 2 in which the anionic synthetic nonsoap detergent is in the form of the organic amine salt. Detergency Redeposltion 6. A light duty detergent composition in accordance Units Units wlth claim 2 in which the anionic synthetic nonsoap detergent is in the form of the sodium salt.

7. A light duty detergent composition in accordance with claim 2 in which the anionic synthetic nonsoap detergent is in the form of the ammonium salt.

8. A light duty detergent composition in accordance with claim 2 in which the synthetic nonsoap detergent is a nonionic syndet.

9. A light duty detergent composition in accordance with claim 8 in which the no-nionic synthetic nonsoap detergent is a detergent polyoxyalkylene ether.

10. A light duty detergent composition in accordance with claim 8 in which the nonionic synthetic nonsoap detergent is a polyoxyalkylene ether glycol.

position aerate? 11. A light duty detergent composition in accordance with claim 8 in which the nonionic synthetic nonsoap detergent is a polyoxyalkylene alkyl phenol.

12. A concentrated light duty liquid detergent comwhich remains clear and uniform Without separation of solid materials at low temperatures consisting essentially of an aqueous solution of synthetic organic nonsoap detergent selected from the group consisting of anionic and nonionic synthetic organic nonsoap detergents in an amount within the range from about 15% to about 50% to impart detergency to the solution and fl,'-decylamino-bis-ethanolpropionarnide in an amount within the range from about 2 to about 10% by weight of the syn- "1'2 thetic nonsoap detergent to enhance the sudsing and detergency of the synthetic nonsoap detergent.

13. A concentrated light duty liquid detergent composition in accordance with claim 12 which contains ethyl alcohol.

References Cited in the tile of this patent UNITED STATES PATENTS 

1. A LIGHT DUTY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SYNTHETIC ORGANIC NONSOAP DETERGENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC AND NONIONIC SYNTHETIC ORGANIC NONSOAP DETERGENTS AND AN AMOUNT WITHIN THE RANGE FROM ABOUT 2 TO ABOUT 10% BY WEIGHT OF THE SYNTHETIC NONSOAP DETERGENT OF B,B''-DECYLAMINOBISETHANOLPROPIONAMIDE TO ENHANCE THE DETERGENCY AND SUDSING OF THE SYNTHETIC NONSOAP DETERGENT. 